CN114457386A - Method for electrolyzing aluminum by inert anode treatment - Google Patents
Method for electrolyzing aluminum by inert anode treatment Download PDFInfo
- Publication number
- CN114457386A CN114457386A CN202210026504.5A CN202210026504A CN114457386A CN 114457386 A CN114457386 A CN 114457386A CN 202210026504 A CN202210026504 A CN 202210026504A CN 114457386 A CN114457386 A CN 114457386A
- Authority
- CN
- China
- Prior art keywords
- anode
- inert
- silicon carbide
- aluminum
- electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 43
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- 238000007789 sealing Methods 0.000 claims abstract description 17
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 description 12
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- -1 oxygen anions Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000008619 Xingren Substances 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
Abstract
The invention relates to an electrolytic aluminum method containing inert anode treatment, the method of the invention is firstly to prepare a semi-inert or complete inert anode, the semi-inert anode has stronger stability than the existing carbon anode, and a large amount of oxygen released on the anode is not quickly corroded and oxidized when the aluminum is electrolyzed; the anode adopts a P-type conductive semiconductor silicon carbide ceramic material with a large number of cavities, so that the inertia of the anode is protected, and the service life of the anode is prolonged; the method adopts the platinum metal sealing ring to protect the interfaces among the silicon carbide anode, the cryolite solution and the upper space of the electrolytic bath, thereby prolonging the service life of the most easily damaged part. The part above the cryolite liquid level of the electrolytic cell is sealed, oxygen generated by electrolytic aluminum in the electrolytic cell is pumped away in time, contact between excessive oxygen and a high-temperature silicon carbide electrode is avoided, and the service life of the anode is prolonged.
Description
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to an aluminum electrolysis method with inert anode treatment.
Background
Two thirds of the electrolytic aluminum production in China is achieved in the world, and the most advanced electrolytic aluminum technology of 530kA is also applied in China on a large scale. The chinese technical level of electrolytic aluminum represents the most advanced technical level of electrolytic aluminum in practice. In the process of electrolyzing aluminum, an electrolytic anode is in a very severe environment at a high temperature (900 ℃ C. and 950 ℃ C.), and a large amount of active oxygen atoms with strong oxidizing property are generated by the anode in the process of electrolyzing aluminum and can generate oxidation reaction with an anode material. The anode which is mature in application at present is a carbon anode, and the carbon anode has the advantages of low price, high temperature resistance, no melting and no oxidation, and can directly react with the produced active oxygen atoms to generate carbon dioxide anode gas to be discharged, so that the carbon emission in the atmosphere is increased. Meanwhile, the carbon anode can bring in a plurality of hydrogen elements and can be combined with fluorine in the electrolyte to form hydrogen fluoride polluted gas.
A large number of inert anodes for electrolytic aluminium have been developed by the national institute of research, university of imitation foreign technology, in SnO2Adding ZnO, CuO and Fe2O3、Sb2O3、Bi2Metal oxide ceramic anodes of O, NiFe2O4+ NiO + Cu containing 17% Cu and 51.7% NiO + 48.3% Fe2O3Anode of (2), NiFe2O4+ NiO + Cu + Ag ferrite (e.g. NiFe)2O4Or ZnFe2O4) And a ceramic phase of spinel structure of metal oxide (such as NiO or ZnO) and a Cu-Ag alloy phase. (iii) Fe-Ni-Al2O3Cermet type inert anodes and the like have not entered practical use although they have been reported in the laboratory to be effective.
The prior inert anode electrolytic aluminum technology has no practicability, the most advanced 530kA Xingren adopted in China is the research of the ascending aluminum industry, the electrolytic aluminum anode adopted by the former is still a carbon anode, the prior art is not put into practical use, the subversive technical revolution generated by the inert anode electrolytic aluminum is not exerted, the specific economic benefit is not generated, and the service life of the electrode is short.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an aluminum electrolysis method with inert anode treatment, which can greatly prolong the service life of an anode of the electrolytic aluminum and does not generate polluting gas in the aluminum electrolysis process, thereby improving the economic efficiency of production and having stronger practicability and operability.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aluminum electrolysis process comprising an inert anode treatment comprising the steps of:
(1) preparing a semi-inert or fully inert anode;
(2) buckling a platinum metal sealing ring among the interfaces of the anode, air and the cryolite solution;
(3) the electrolytic bath is closed, and the generated oxygen is pumped away in time.
Further, the semi-inert anode in the step (1) is prepared by coating a layer of silicon carbide on the surface of the carbon electrode.
Further, the thickness of the silicon carbide is more than 1 mm.
The semi-inert anode can be oxidized and corroded in a proper range, the semi-inert anode is not required to be consumed all the time, the semi-inert anode has stronger stability than the existing carbon anode, can be electrolyzed in cryolite solution at the temperature higher than 900 ℃, can not be quickly corroded and oxidized when a large amount of oxygen is released, the electrode consumption speed is far lower than that of the carbon anode, the semi-inert anode can greatly save carbon on the basis of the carbon anode, practical and very high economic efficiency is generated, and the semi-inert anode is slowly perfected and improved into a complete inert anode under the condition of gradually improving the production benefit of enterprises.
Further, the completely inert anode in the step (1) is a semiconductor ceramic material prepared by sintering P-type aluminum-doped silicon carbide.
Furthermore, the doping proportion of the aluminum is 0.1-1%.
Further, the sintering temperature is 1700-1900 ℃.
Further, the sintering temperature was 1800 ℃.
The completely inert anode in the invention is the anode of input current in the electrolytic process, and a large amount of electrons enter the anode from the electrolyte. The P-type conductive semiconductor containing a large number of holes is adopted as the silicon carbide ceramic material anode, so that electrons on the surface of the anode can be quickly compounded with the holes, and the electrons enter the anode of the power supply through hole conduction to accelerate oxygen anions to discharge to generate oxygen atoms, thereby quickly generating oxygen for release. The anode is in a state of lacking electrons all the time, so that the inertia of the anode is protected, the service life of the anode is prolonged, new impurity elements cannot be brought into the P-type semiconductor formed by aluminum doping, and the P-type semiconductor is superior to other P-type semiconductors formed by doping of trivalent elements.
Silicon carbide is a very stable covalent compound, ideally, silicon carbide forms stable covalent bonds with four adjacent carbon atoms per silicon atom, and the compound has very strong chemical stability. The silicon carbide has high heat conductivity coefficient, small thermal expansion coefficient and small thermal stress when used as an electrode. Silicon carbide has at least 70 crystal forms. The alpha-silicon carbide isomorphism is formed at a high temperature of more than 2000 ℃, and has a hexagonal crystal structure (like wurtzite). Beta-silicon carbide is produced in a cubic crystal system at a temperature below 2000 ℃. mu-SiC is the most stable and gives a relatively pleasant sound at impact. The silicon carbide with the three structures can keep strong stability and oxidation resistance in the cryolite solution at the temperature higher than 900 ℃. The existing production workshop of the carbon anode can produce the silicon carbide semiconductor ceramic anode with the surface of the P-type silicon carbide semiconductor ceramic on the outside and the carbon semi-inert silicon carbide anode on the inside only by little change.
Aiming at serious corrosion and oxidation of silicon carbide, cryolite solution at the temperature higher than 900 ℃ and air interface, the invention adopts the platinum sealing ring to protect the interface and avoids excessive oxygen from contacting with the high-temperature silicon carbide inert electrode.
Further, the air pressure above the electrolytic bath in the step (3) is controlled to be 1-100 Pa.
In the invention, the part above the liquid level of cryolite in the electrolytic tank is sealed, the inside of the electrolytic tank is pumped into a low-pressure environment with the pressure of 1-100Pa by a mechanical pump, and although a high vacuum degree is not required, the generated oxygen is pumped away in time by the mechanical pump to form the low-pressure environment, so that the speed of oxygen generated by the anode to corrode the anode can be reduced, the service life of the anode is prolonged, and the production economic efficiency is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method of the invention prepares the semi-inert or completely inert anode, the semi-inert anode of the invention has stronger stability than the existing carbon anode, can be electrolyzed in the cryolite solution with the temperature higher than 900 ℃, can not be quickly corroded and oxidized when releasing a large amount of oxygen, the electrode consumption speed is far lower than that of the carbon anode, and the multiple inert anodes can greatly save carbon on the basis of the carbon anode and generate practical and great economic efficiency; the completely inert anode in the invention is the anode of input current in the electrolytic process, and a large amount of electrons enter the anode from the electrolyte. A large number of hole-conductive P-type semiconductors are used as the anode, so that electrons on the surface of the anode can be quickly compounded with holes, and the electrons enter the anode of the power supply through hole conduction to accelerate oxygen anions to discharge to generate oxygen atoms, so that oxygen is quickly generated and released. The anode is in a state of lacking electrons all the time, so that the inertia of the anode is protected, the service life of the anode is prolonged, and the P-type semiconductor formed by doping aluminum does not bring new impurity elements, so that the anode is more superior to the P-type semiconductor formed by doping other trivalent elements;
(2) the method adopts the platinum metal sealing ring for protection, avoids excessive oxygen from contacting with the high-temperature silicon carbide silicon electrode, seals the part above the liquid level of the cryolite of the electrolytic tank, pumps the inside into a low-pressure environment by a mechanical pump, and can reduce the speed of oxygen generated by the anode to corrode the anode, thereby prolonging the service life of the anode and improving the production economic efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
An aluminum electrolysis process comprising an inert anode treatment comprising the steps of:
(1) the semi-inert anode is prepared by coating a layer of silicon carbide on the surface of a carbon electrode, and the thickness of the silicon carbide is 1.1mm, the semi-inert anode has stronger stability than the existing carbon anode, can be electrolyzed in cryolite solution at the temperature higher than 900 ℃, is not quickly corroded and oxidized when releasing a large amount of oxygen, and has the electrode consumption speed far lower than that of the carbon anode;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic bath is sealed, oxygen generated in the electrolytic bath is pumped away in time by a mechanical pump, the pressure is 1Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Example 2
An aluminum electrolysis process comprising an inert anode treatment comprising the steps of:
(1) the semi-inert anode is prepared by coating a layer of silicon carbide on the surface of a carbon electrode, and the thickness of the silicon carbide is 2mm, the semi-inert anode has stronger stability than the existing carbon anode, can be electrolyzed in cryolite solution at the temperature higher than 900 ℃, is not quickly corroded and oxidized when releasing a large amount of oxygen, and has far lower electrode consumption speed than the carbon anode;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic bath is sealed, oxygen generated in the electrolytic bath is pumped away in time by a mechanical pump, the pressure is 50Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Example 3
An aluminum electrolysis process comprising an inert anode treatment comprising the steps of:
(1) the semi-inert anode is prepared by coating a layer of silicon carbide on the surface of a carbon electrode, and the thickness of the silicon carbide is 2.5mm, the semi-inert anode has stronger stability than the existing carbon anode, can be electrolyzed in cryolite solution at the temperature higher than 900 ℃, is not quickly corroded and oxidized when releasing a large amount of oxygen, and has the electrode consumption speed far lower than that of the carbon anode;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic tank is sealed, oxygen generated in the electrolytic tank is pumped away in time by a mechanical pump, the pressure is 100Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Example 4
An aluminum electrolysis process comprising an inert anode treatment comprising the steps of:
(1) preparing a complete inert anode, wherein the complete inert anode is a semiconductor ceramic material prepared by sintering P-type aluminum-doped silicon carbide, the doping proportion of aluminum is 0.1%, the sintering temperature is 1700 ℃, the complete inert anode is a positive electrode for inputting current in the electrolytic process, and a large amount of electrons enter the anode from electrolyte. A large number of hole-conductive P-type semiconductors are used as anodes, so that electrons on the surfaces of the anodes can be rapidly compounded with holes, the electrons enter the positive electrode of a power supply through hole conduction, oxygen atoms generated by oxygen anion discharge are accelerated, and oxygen release is rapidly generated;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic bath is sealed, oxygen generated in the electrolytic bath is pumped away in time by a mechanical pump, the pressure is 1Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Example 5
(1) Preparing a complete inert anode, wherein the complete inert anode is a semiconductor ceramic material prepared by sintering P-type aluminum-doped silicon carbide, the doping proportion of aluminum is 0.55%, the sintering temperature is 1800 ℃, the complete inert anode is a positive electrode for inputting current in the electrolytic process, and a large amount of electrons enter the anode from electrolyte. A large number of hole-conductive P-type semiconductors are used as anodes, so that electrons on the surfaces of the anodes can be rapidly compounded with holes, the electrons enter the positive electrode of a power supply through hole conduction, oxygen atoms generated by oxygen anion discharge are accelerated, and oxygen release is rapidly generated;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic bath is sealed, oxygen generated in the electrolytic bath is pumped away in time by a mechanical pump, the pressure is 50Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Example 6
(1) Preparing a complete inert anode, wherein the complete inert anode is a semiconductor ceramic material prepared by sintering P-type aluminum-doped silicon carbide, the doping proportion of aluminum is 1%, the sintering temperature is 1900 ℃, the complete inert anode is a positive electrode for inputting current in the electrolytic process, and a large amount of electrons enter the anode from electrolyte. A large number of hole-conductive P-type semiconductors are used as anodes, so that electrons on the surfaces of the anodes can be rapidly compounded with holes, the electrons enter the positive electrode of a power supply through hole conduction, oxygen atoms generated by oxygen anion discharge are accelerated, and oxygen release is rapidly generated;
(2) the platinum metal sealing ring is buckled among the interfaces of the anode, air and cryolite melt, and because the silicon carbide, the cryolite melt with the temperature higher than 900 ℃ and the air interface are corroded and oxidized seriously, the platinum metal sealing ring is adopted for protection in the invention, so that the contact of excessive oxygen and the high-temperature silicon carbide electrode is avoided;
(3) the part above the liquid level of cryolite in the electrolytic tank is sealed, oxygen generated in the electrolytic tank is pumped away in time by a mechanical pump, the pressure is 100Pa, a low-pressure environment is formed, and the speed of oxygen generated by the anode to corrode the anode can be reduced, so that the service life of the anode is prolonged, and the production economic efficiency is improved.
Test example 1
The test groups were subjected to an electrolytic aluminum test using the anodes of electrolytic aluminum treated by the methods of examples 1 to 6, and the comparative group was subjected to an electrolytic aluminum test using a carbon anode under the same conditions, and the service life of the anode was examined, and the results are shown in Table 1.
TABLE 1
It can be seen from the table that the anodes treated by the method of the present invention have significantly increased service life compared to existing carbon anodes, and that the use of fully inert anodes has a longer life than semi-inert anodes.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. An aluminum electrolysis process comprising an inert anode treatment, comprising the steps of:
(1) preparing a semi-inert or fully inert anode;
(2) buckling a platinum metal sealing ring among the interfaces of the anode, air and the cryolite solution;
(3) the electrolytic bath is closed, and the generated oxygen is pumped away in time.
2. The method of claim 1, wherein the semi-inert anode is prepared by coating a surface of the carbon electrode with a layer of silicon carbide in step (1).
3. The method of claim 2 wherein the silicon carbide has a thickness of > 1 mm.
4. The inert anode treatment-containing electrolytic aluminum method according to claim 1, wherein the completely inert anode in the step (1) is a semiconductor ceramic material prepared by sintering silicon carbide doped with aluminum in P-type.
5. The method of claim 4, wherein the aluminum is doped in an amount of 0.1 to 1%.
6. The method of claim 4 wherein the sintering temperature is 1700-1900 ℃.
7. The method of claim 6 wherein the sintering temperature is 1800 ℃.
8. The method of electrolyzing aluminum containing inert anode treatment according to claim 1, wherein the air pressure over the electrolytic bath in the step (3) is controlled to be 1 to 100 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210026504.5A CN114457386B (en) | 2022-01-11 | 2022-01-11 | Electrolytic aluminum method containing inert anode treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210026504.5A CN114457386B (en) | 2022-01-11 | 2022-01-11 | Electrolytic aluminum method containing inert anode treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114457386A true CN114457386A (en) | 2022-05-10 |
| CN114457386B CN114457386B (en) | 2024-04-16 |
Family
ID=81409463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210026504.5A Active CN114457386B (en) | 2022-01-11 | 2022-01-11 | Electrolytic aluminum method containing inert anode treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114457386B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB625861A (en) * | 1942-02-23 | 1949-07-05 | Norske Elektrokemisk Ind As | Improvements relating to anode protection in electrolytic cells for the production of aluminium |
| US4216071A (en) * | 1977-03-04 | 1980-08-05 | Energietechnik GmbH Studiengesellschaft fur Energie-Umwandlung- , -Fortleitung und -Anwendung | Electrodeposition cell |
| US4257855A (en) * | 1978-07-14 | 1981-03-24 | Solomon Zaromb | Apparatus and methods for the electrolytic production of aluminum metal |
| US4543174A (en) * | 1983-02-16 | 1985-09-24 | Eltech Systems Corporation | Method of making a catalytic lead-based oxygen evolving anode |
| CA1305942C (en) * | 1986-02-28 | 1992-08-04 | Jimmie R. Hodges | Electrolytic cell with aluminum anode with titanium sheath and precious metal coating |
| US5286353A (en) * | 1991-06-04 | 1994-02-15 | Vaw Aluminium A.G. | Electrolysis cell and method for the extraction of aluminum |
| US20110192728A1 (en) * | 2008-09-08 | 2011-08-11 | Rio Tinto Alcan International Limited | Metallic oxygen evolving anode operating at high current density for aluminium reduction cells |
| CN102953084A (en) * | 2011-08-24 | 2013-03-06 | 贵阳铝镁设计研究院有限公司 | Aluminum reduction cell with plate-shaped diaphragm structure |
| CN103014769A (en) * | 2012-11-26 | 2013-04-03 | 中国铝业股份有限公司 | Alloy inert anode for aluminium electrolysis and preparation method thereof |
| CN103320817A (en) * | 2013-07-09 | 2013-09-25 | 中国铝业股份有限公司 | Preparation method of heat-preserving and sealing structure above hearth of inert electrode aluminum electrolyzing tank |
| CN105274470A (en) * | 2014-07-10 | 2016-01-27 | 北京航空航天大学 | Rare earth-copper-nickel-chromium multi-element co-penetration treatment method for electrolytic aluminum anode steel claw protection ring |
| CN207537548U (en) * | 2017-11-10 | 2018-06-26 | 聊城信源集团有限公司 | A kind of electrolytic aluminum anode heat-preserving cover plate |
| CA3073388A1 (en) * | 2020-02-20 | 2021-08-20 | Concordia University | A method of fabrication of inert anodes |
-
2022
- 2022-01-11 CN CN202210026504.5A patent/CN114457386B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB625861A (en) * | 1942-02-23 | 1949-07-05 | Norske Elektrokemisk Ind As | Improvements relating to anode protection in electrolytic cells for the production of aluminium |
| US4216071A (en) * | 1977-03-04 | 1980-08-05 | Energietechnik GmbH Studiengesellschaft fur Energie-Umwandlung- , -Fortleitung und -Anwendung | Electrodeposition cell |
| US4257855A (en) * | 1978-07-14 | 1981-03-24 | Solomon Zaromb | Apparatus and methods for the electrolytic production of aluminum metal |
| US4543174A (en) * | 1983-02-16 | 1985-09-24 | Eltech Systems Corporation | Method of making a catalytic lead-based oxygen evolving anode |
| CA1305942C (en) * | 1986-02-28 | 1992-08-04 | Jimmie R. Hodges | Electrolytic cell with aluminum anode with titanium sheath and precious metal coating |
| US5286353A (en) * | 1991-06-04 | 1994-02-15 | Vaw Aluminium A.G. | Electrolysis cell and method for the extraction of aluminum |
| US20110192728A1 (en) * | 2008-09-08 | 2011-08-11 | Rio Tinto Alcan International Limited | Metallic oxygen evolving anode operating at high current density for aluminium reduction cells |
| CN102953084A (en) * | 2011-08-24 | 2013-03-06 | 贵阳铝镁设计研究院有限公司 | Aluminum reduction cell with plate-shaped diaphragm structure |
| CN103014769A (en) * | 2012-11-26 | 2013-04-03 | 中国铝业股份有限公司 | Alloy inert anode for aluminium electrolysis and preparation method thereof |
| CN103320817A (en) * | 2013-07-09 | 2013-09-25 | 中国铝业股份有限公司 | Preparation method of heat-preserving and sealing structure above hearth of inert electrode aluminum electrolyzing tank |
| CN105274470A (en) * | 2014-07-10 | 2016-01-27 | 北京航空航天大学 | Rare earth-copper-nickel-chromium multi-element co-penetration treatment method for electrolytic aluminum anode steel claw protection ring |
| CN207537548U (en) * | 2017-11-10 | 2018-06-26 | 聊城信源集团有限公司 | A kind of electrolytic aluminum anode heat-preserving cover plate |
| CA3073388A1 (en) * | 2020-02-20 | 2021-08-20 | Concordia University | A method of fabrication of inert anodes |
Non-Patent Citations (1)
| Title |
|---|
| 于先进等: "铝电解用碳化硅涂层惰性阳极的制备与性能研究", 《中国稀土学报》, vol. 26, pages 435 - 438 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114457386B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108911052B (en) | Doped titanium dioxide electrode and preparation method and application thereof | |
| JP4927006B2 (en) | Cathode for hydrogen generation | |
| JP4673628B2 (en) | Cathode for hydrogen generation | |
| TWI490371B (en) | Electrode for electrolytic applications | |
| CN111170415A (en) | Titanium oxide/ruthenium oxide composite electrode and preparation method and application thereof | |
| JP4341838B2 (en) | Electrode cathode | |
| CN102268689A (en) | Titanium-based oxide acid resistant anode and preparation method thereof | |
| CN103820816B (en) | A kind of surface treatment method of aluminum electrolysis inertia anode | |
| CN102762776B (en) | Activated cathode for hydrogen evolution | |
| CN101388457A (en) | Aluminum alloy anode material for battery | |
| CN103014769A (en) | Alloy inert anode for aluminium electrolysis and preparation method thereof | |
| CN104878354A (en) | Coating for flat-plate intermediate-temperature solid oxide fuel cell metal connector | |
| CN106702431A (en) | Anti-oxidation coating for carbon anodes in aluminum electrolysis | |
| CN1073641C (en) | Oxidation-resistant metallic material | |
| CN110318069B (en) | Electrode for electrolysis, method for producing same, and electrolytic cell | |
| CN113061926A (en) | Titanium dioxide anode diffusion layer for PEM water electrolysis cell and preparation method and application thereof | |
| CN103482625B (en) | A kind of preparation method of niobium carbide and carbonization tantalum electrode | |
| CN107740143A (en) | A kind of iron-based inert anode with ferrous acid lithium diaphragm and preparation method thereof, application | |
| CN106906491A (en) | A kind of ferronickel base is anti-oxidant and corrosion resisting alloy inert anode material | |
| CN114457386B (en) | Electrolytic aluminum method containing inert anode treatment | |
| Liu et al. | Effect of molar ratio of ruthenium and antimony on corrosion mechanism of Ti/Sn-Sb-RuOx electrode for zinc electrowinning | |
| CN103628060B (en) | New electrode materials of molybdenum+depositing titanium nitride and preparation method thereof is oozed on a kind of surface | |
| CN108998807A (en) | A kind of improved Ru-Ce coated electrode | |
| CN113185857B (en) | Graphite anode plate antioxidant coating composition and application thereof | |
| CN114182301A (en) | Method for preparing metal beryllium by electrolyzing beryllium oxide through fluoride molten salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |